Hexachloro-5-phenyldiamine bicyclo-(2.2.1)-2-heptene



United States Patent f .6.;Claims. (Cl. 26057.8)

This invention relates to the production of new compositions of matter. -More .specifically, the present invention relates to the production of new halogenated diamines-Which are useful .inthe production. of =fire resistant cured epoxy resins. ;The composition of the presentinvention has the structure:

01 .NH; Cl l welfa Ha oi l 11 NH:

Cl H

and is termed .a 1,2,3,4,7,7-hexachloro --phenyldiaminebicyclo (2.2.l)-2-heptene.

The compound of thetpresent invention isusefulas a curingagentforepoxy resins, containing epoxide. groups. In particular, resins which are formed by aqueousalkaline condensation of epichlorohydrin andbisphenol are advantageously cured by the; product of thev present inven- -tion.

,While diamines have heretofore been usedas condensa- 1 tion or curing agents with epoxy resins, they have in general been hydrocarbon diamines such.,.,as} phenylene Q diamine, and ,the. epoxy resins which were, cured there- -.-with; are flammableand do nothave adequate-heat resistance.

.In addition to their .use, as curingagents, {thenew compositions of, the, present invention have utility, as, fungit'cides, miticides. and insecticides.

. Itis therefore an object of, this invention to.,prepare mew. compositions ofmatter, usefulin tlie produotion of ;polymeric materials.

Another. objectpf this invention is-thepreparation of :new halogenated compositions v of. matter.

Z Still another objector this invention. is the preparation (of new halogenated .diainines.

Still another ,objectpfi .this invention is the preparation of insecticidallyvactive compositions of matter.

Other objects, features andadvantages of the present invention will become apparent from the following description.

Thecompositions of t hepresentinvention are useful to produce cured epoxyresinswhich are fire and heat resistant andhaye excellentphysical properties as regards strength, crush resistance, vimpact resistance,i dielectric strength, and the like.

Epoxy resins ,curedwith the diamine ofhthe present invention are useful as potting resins, casting resins, dip resins, saturants for.;fiberglass, electrical insulators and thelike where fire and heat resistant propertiesare especially desirable.

The cure ofepoxy, resins .as vahovedescribed takes place with other well-known. diamines by reaction of .the amine hydrogenswith theepoxidegroups. Mixtures ofthefdiamines of thepresent invention and the, epoxy resins have relatively long pot. lives,,, an advantageous feature for-certain applications.

The compositions of the present invention are solids 2,9 01 ,5 l a Retai er Au .2 195.9

and as such are particularly well suited for use as curing agents for epoxy resins, since liquid and more volatile diamines could not readily be used at elevated temperatures without added hazard of toxic'fumes. 4 In addition, the compositions of the presentinvention have utility as insecticides, rniticides and fungicides.

The halogenated diamin'es of the present invention may bernade by several methods. One mode of preparation involves the redilction of the corresponding dinitrophenylhexachlorobicycloheptene by one of the means known to the artffor :the reduction of dinitro compounds. The g l dinitropheiiyl adduct may be prepared by nitration of the Diels-Alderadductiof hexachIo rocyclopentadiene and styrene. The 3 ,4-dinitrophenyl-hexachlorocyclopentadiene adduct andthe .3,5-dinitrophenyl-hexachlorocyclopentadiene adduct maybe prepared by adducting 3- nitrostyrene and hexachlorocyclopentadiene, nitrating the I dduct, and recovering the desired product by fractional i stallization. i

Another method for the preparation of the diamines of the l'present invention involves reacting a dichloro styrene withammonia, adducting the resulting diainino styrene with ,hexachlorocyclopentadiene,' and recovering theiproduct of the compositionfof the present invention.

Tlni's, by starting with 3,'5-di'chlorostyrene,arnrnoniating hand adductingthe product thereof in a Diels-Alder Y manner with.hexachlorocyclopentadiene, the 3-5-diarninoipheny ll,2,3, f,7;7hexachlorobicyclo '(2.2.1')-2-heptene is recovered as the product.

"The aforementioned adductions are carried out using hexachloro'cyclopentadien'e reactant as a solvent, and

the I the addiiction temperatures may vary'from' about 70, C. tqabout 22.0 C. Theratio of reactants should be at least equimolar but an excessof hexachlorocyclopentadi- Jena can be used as solvent; or, if desired, other inert soly ents mayjalso be utilized. However, the use of addi- ,ti nabsolvents is neither: necessary nor preferred. The

adduction' time will vary with-the temperature and e rhi b i -aensra lr ttqmi bqv 3- mi er' 9 "ilheicil ewinaexamp e w llust a t err p ot the dianiinou compounds of the present invention? .EXMiPE. I Adduction 0f hexach lorocyclopentadiene and styrene grams of crystals with a meltingpoint of 73.0-74.0" C.

were obtained.

EXAMPLE II Nit ra fi0n of hexachlorocyclopentadiene-styrene adduct l, 005 grams- (2.66 moles) of the hexachlorocyclopentadiene-styrene adduct prepared in Example I and 1700 ml. of concentrated sulfuric acid (specific gravityl.84) were added to a glass reaction vessel equipped with stir- ,.rer,-, thermometer, reflux condenser and heatingmantle.

The mixture was then heated to 85 C. and while con- (cinuously stirring, 750 ml. of fuming nitric acid (specific lgrarzity-LSO) were added uniformly over a two-hour period. During thenitric acid addition, the temperature was maintained at 8590 C. by means of external cooling. An additional 150 ml. of fuming nitric acid were 1 added while maintaining the reaction mixture at --1l:0

C. The reaction mixture was kept at this temperature for 6 hours after the completion of the addition. At the end of the six-hour period, it was cooled, the acid fraction decanted and the solid product washed with water. It was then washed with sodium bicarbonate solution and water, air dried, and recrystallized from isopropyl alcohol. Hexachlorocyclopentadiene-2,4-dinitrostyrene adduct (923 g.) with a melting point of 180.5-182 C. was

obtained. The pure product was analyzed for Theoretical Found EXAMPLE III Reduction of product of Example II to the desired diamine composition 1,2,3,4,7,7 hexachloro 5 (2,4-dinitrophenyl)-bicyclo (2.2.1)-2-heptene (95 g.; 0.203 moles) prepared in Example II and benzene (400 ml.) were added to a glass reaction vessel equipped with stirrer, thermometer, re-

flux condensor and heating mantle. Water (50 g.) was added to the mixture which then was heated to reflux temperature. With vigorous stirring, iron powder (200 g.) reduced by hydrogen was added over a period of 15-20 minutes. Concentrated hydrochloric acid (50 ml.) was then added dropwise over a period of one hour after which the reaction mixture was maintained at the reflux temperature for an additional three hours. The hot mixture was filtered, washed with benzene, and the wash Theoretical Found EXAMPLE IV Into a 100 ml., 3-necked flask equipped with reflux condenser, stirrer and dropping funnel was placed hexachlorocyclopentadiene (0.1 mole; 27.3 g.) and t-butyl catechol (0.1 g.). The material was maintained at a temperature of 125l30 C. and m-nitro styrene (14.9 g.; 0.1 mole) containing t-butyl catechol (0.1 g.) was added dropwise through the dropping funnel to the warm reaction mixture over a one-hour period. After addition was complete the mixture was heated an additional half hour. The reaction mixture was then dissolved in 95% ethanol, filtered and cooled. Thirty-five grams of crystalline material, melting at 108109 C. were recovered. Recrystallization from ethyl acetate gave a product melting at 111.5112.0 C.

EXAMPLE V Preparation of the 5-(2,5-diaminophenyl)-hexachl0r0 bicycloheptene Hexachlorocyclopentadiene-m-nitro-phenylstyrene adduct (1125 g.; 2.66 moles) prepared in Example IV and concentrated sulfuric acid (50 ml.) (specific gravity- 1.84) is added to a glass reaction vessel equipped with stirrer, thermometer, reflux condenser and heating mantle.

7 ethanol filtered and cooled. The product recrystallized from ethyl acetate is substantially pure 1,2,3,4,7,7hexa- Preparation The mixture is then heated to C. and while continuously stirring 375 ml. of fuming nitric acid (specific gravity-1.50) are added uniformly over a two-hour period. During the nitric acid addition, the temperature is maintained at 85-90 C. by means of external cooling. An additional 75 ml. of fuming nitric acid are added while keeping the reaction mixture of -110" C; The mixture is maintained at this temperature for six hours after the completion of the addition. At the .end of the six-hour period, the reaction mixture is cooled,

the acid fraction decanted, and the solid product washed with Water. By fractional crystallization the desired 1,2,3,4,7,7 hexachloro 5 (2,5 dinitrophenyl) bicyclo (2.2.1)-2heptene is obtained. Reduction of the above product as described in Example III results in a fine crystalline material which on recrystallization from heptane is identified as substantially pure 1,2,3,4,7,7 hexachloro 5 (2,5 diaminophenyl) bicyclo-(2.2.l)-2- heptene.

EXAMPLE VI of 1,2,3,4,7,7-hexachloro-5-(3,5-diamin0- phenyl)-bicyclo (2.2.1)-2-heptene 3,5-dichlorostyrene (173 g.; 1.0 mole) liquid ammonia (170.0 g.; 10.0 moles) are placed in a bomb and heated to C. for eight hours. The product recovered from the bomb at the completion of the am monolysis is 3,5-diaminostyrene. This substituted styrene is then adducted with hexachlorocyclopentadiene in a Diels-Alder manner as follows:

Into a 100 ml., 3-necked flask equipped with reflux condenser, stirrer and dropping funnel is placed hexachlorocyclopentadiene (27.4 g.; 0.1 mole) and t-butyl catechol (0.1 g.). The material is maintained at a temperature of 130 C. and 3,5-diaminostyrene (13.4 g.; 0.1 mole) containing 0.1 g. t-butyl catechol is added dropwise through the dropping funnel to the warm reaction mixture over a one-hour period. After addition is complete, the mixture is heated an additional half hour. The reaction mixture is then dissolved in 95% chlorobicyclo 5 (3,5-diaminophenyl)-bicyclo-(2.2.1)-2- heptene.

It should be noted that this new compound of Example VI can also be prepared by the aforementioned method of reduction of the corresponding dinitro compound, a method applicable to the preparation of all of the 1,2,3,4,7,7 hexachlorobicyclo-S-(diaminophenyl)-bicyclo (2.2.1)-2-heptenes of the present invention. Thus, by reduction of the 3,4-dinitrophenyl composition, the product will be the 3,4-diaminophenyl; reduction of the 2,6- dinitrophenyl will produce the 2,6-diamine; etc.

The diamines of the present invention are useful in curing epoxy resins and in particular are useful in curing epoxy resins which are derived from condensation of epichlorohydrin and bis-phenol. Other epoxides which are not resins in themselves can also be cured to resinous Generally, the product of the present invention is useful in curing liquid epoxy resins such as above described. Exemplary of such resins is a product sold under the trade name of Epon 828 which is a liquid having an epoxide equivalent of 1 mole for about 200 grams of resin. Other amines such as phenylene diamine have been used commercially for such applications.

The amount of diamine utilized is calculated from the number of moles of epoxide available either in the compound or in the epoxy resin. For example, with diamines in general mole is required to cure one mole of epoxide. As above illustrated, the liquid epoxy resins have The following example will illustratethe procedure and method of curing an epoxy resin withthepresent novel diami'ne compound:

densation of epichlorohydrin and bisfphenol "(sold u'nder trade name Epon 828) was added 357 -gr'am'sof the diamine prepared in Example III. The reactants were mixed with heating at about 90-100 C. and poured into a test tube. The test tube was maintained at 9S-100 C. for three hours, at which time the mixture was substantially hard. Further heating at 100 C. for ten hours had no apparent effect. The temperature was then raised to 150 C. at which temperature the cured epoxy resin was resistant to deformation. The resin was fire resistant and was self-extinguishing after removal from an oxidizing flame.

The mixing operation is standard procedure and since the diarnine is solid, warming is necessary to obtain adequate mixing of the reactants. The rate of cure of the epoxy resins with the diamine of the present invention varies in an inverse manner with the temperature of cure. Thus, at higher temperatures, the cure is complete to hardness in a shorter time than at lower temperatures.

These fire resistant epoxy resins are useful as potting resins for electrical elements such as coils. They are resistant to heat and also resistant to burning, which is especially valuable in electrical applications, but which may also be utilized in other industrial applications.

As previously discussed, the compositions of the present invention are solids which have a rather low vapor pressure. Liquid diamines and some solid diamines used for curing epoxy resins are rather volatile and present a toxic hazard in view of this volatility. The present compounds low volatility reduces this well-known toxic hazard a considerable degree and makes industrial handling somewhat safer than is ordinarily possible.

In addition to their aforementioned utility as a curing agent, the new compositions have value as miticites, fungicides and insecticides as shown in the following tables:

TABLE 1 Miticide test The 1,2,3,4,7 ,7-hexachloro-5-(2,4 diaminophenyD-bicyclo (2.2.1)-2-heptene was formulated as a 10% wettable powder, dispersed in water at a concentration of 0.4% actual compound and applied by dipping mite-infested cranberry bean plants therein.

72 Hours After Treatment Percent Plant Mortality Injury 1,2,3,4,7 ,7 -hexachlor 5 (2,5 -diaminophenyl)- bicycle (2.2.1)-2-heptene 71.4 0 Untreated 0 0 TABLE 2 Insecticide test TKEIIE Fungicide test Measured quantitiesfof spores were placed on glass slides in contact with the cbmp oiihd being tested. Percentage germination'ofspores'isihen'dfei'mined for each treatment after 24 hours incubation at 72 F.

Percent Spore Germination at Concentrations (P.P.M.) Indicated It is evident from the above data that the compounds of the present invention are unusually versatile, exhibiting a high degree of toxicity to many organisms in addition to their utility as curing agents for epoxy resins. The compounds of the present invention in pesticide applications may be applied and utilized as a sole active ingredient dispersed in carriers such as dusts, solvents, aqueous dispersions or other carriers frequently used in the art. In addition, the compositions of the present in- 'vention can be used in combination with other insecticides and fungicides.

We claim:

1. A compound of the structure:

i 01 01 H H3 Cl H NH,

2. A compound of the structure:

H 01 (31 NH:

H 01c 01 H I C1\|/\H NH, H

3. A compound of the structure:

H NH, 01 01 -H I oiocl H o1 H H NH,

4. A compound of the structure:

H NH;

01 ol l -H 01001 H I o1 H NH, H

5. A compound of the structure:

6. A compound of the sfi'ucture:

References Cited in 1116 file of this patent UNITED STATES PATENTS Polen et a1. Mar. 23, 1954 Polen June 28, 1955 OTHER REFERENCES McBee et al.: Journal of the Chemical Society, vol. 77; p. 388 relied on (1955).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 2,901,510 August 25, 1959 Hyman M. Molotsky, et al It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 2, line '72, for "85- llO read 95===ll0 -==-o Signed and sealed this 23rd day of February 196 (SEAL) Attest:

KARL H. AXLINE ROBERT C. WATSON Commissioner of Patents Attesting Ofiicer 

1. A COMPOUND OF THE STRUCTURE: 